JP3800349B2 - Catalyst composition for removing particulate matter from diesel vehicles - Google Patents

Description

【００３２】
【表２】

【００３３】
１−２．加熱温度による比表面積の変化
前記廃触媒１０ｇずつを取って下記表３のように加熱した後、比表面積を測定し、これを下記表３に示す。
加熱温度４００℃以下では加熱が不充分で不純物が完全に除去されず、１０００℃以上では触媒成分の劣化により気孔が破壊されたことがわかる。
【００３４】
【表３】

【００３５】
１−３．触媒組成物（ＹＫ−Ｒ）粉末の製造
前記廃触媒中の１００ｋｇを炉で２０℃／分の加熱速度で８００℃まで加熱してから２時間加熱してから冷却し、これを粉砕機で粉砕して２００メッシュ粉末を製造した。
【００３６】
実施例２．反応試験（ＹＫ−Ｒ組成物）
２−１．試料準備
前記実施例１−３で製造したＹＫ−Ｒ粉末及びアルミナ、チタニア各１５ｇずつを取ってそれぞれ組成物１（実施用）、組成物２，３（比較用）を準備した。
２−２．ＣＯ酸化反応
前記実施例２−１で製造した組成物試料１〜３に対してそれぞれ反応器に１ｇずつ充填して定着してから反応温度に調節する。ＣＯ２００ｐｐｍを含有した空気を空間速度５０，０００／ｈで反応器に流入させながら反応器出口でＣＯの濃度を時間分解結果で燃焼分析し転換率が５０％になる温度を調査する。
【００３７】
２−３．Ｃ₃ Ｈ₈ 酸化反応
前記ＣＯ酸化反応試験と同方法で１０００ｐｐｍのＣ₃ Ｈ₈ と空気の混合ガスを流入させながらＣ₃ Ｈ₈ の転換率が５０％である温度を測定する。
２−４．ＳＯ₂ 酸化反応
前記ＣＯ酸化反応試験と同方法で５０ｐｐｍのＳＯ₂ と空気の混合ガスを流入させながら４５０℃でＳＯ₂ の転換率を測定する。
【００３８】
２−５．煤煙燃焼試験
前記実施例２−１で製造した組成物試料１〜３をそれぞれ煤煙中の粒子状物質１ｇと均一に混合してから反応器に充填する。温度を分当たり１０℃上昇させて２００℃に到達したら、分当たり１℃ずつ昇温させながら点火される温度（煤煙燃焼温度）を測定した。
前記測定したＣＯとＣ₃ Ｈ₈ の５０％転換率、４５０℃でのＳＯ₂ 転換率及び煤煙燃焼温度を下記表４に示す。
【００３９】
実施例３．高温での耐久性評価
前記実施例２−１で創造した触媒組成物１−３に対してそれぞれ５ｇずつを取って炉に入れた後、２０℃／分の加熱速度で８００℃まで加熱してから５時間放置した。
この触媒組成物を実施例２と同方法でＣＯ、Ｃ₃ Ｈ₈ 、ＳＯ₂ 酸化反応活性と煤煙燃焼温度を測定した結果を下記表４に示す。
【００４０】
実施例４．硫黄酸化物に対する化学的安定性評価
前記実施例２−１で製造した触媒１−３に対して５ｇずつを取って炉に入れた後、２０℃／分の加熱速度で５００℃に加熱し、ＳＯ₃ １００ｐｐｍを含有した窒素ガスを２リットル／分で５０時間流した。
この触媒を実施例２と同方法でＣＯ、Ｃ₃ Ｈ₈ 、ＳＯ₂ 酸化反応活性と煤煙燃焼温度を測定した結果を下記表４に示す。
【００４１】
【表４】

【００４２】
前記表４に示したように、ＹＫ−Ｒ（廃触媒組成物）粉末（試料１）は単独でも煤煙の燃焼性能が優秀であるばかりでなく高温での熱的安定性と硫黄酸化物による化学的安定性が卓越して、実際ディーゼル車両の粒子状物質を除去する触媒組成物として優秀な耐久性を有することがわかる。
【００４３】
実施例５．濾過材製造
５−１．フォーム（Foam) 形濾過材の製造
１０ｐｐｉポリウレタンフォームを２ｃｍ×２ｃｍ×２ｃｍの大きさに切った後、水とメチルアルコールの重量比が１：１である溶液に１０分間担持させた後、乾燥させた。
【００４４】
前記実施例１−３で製造されたＹＫ−Ｒ１００ｇにデキストリン１５ｇをバインダーとして添加した後、モノエタノールアミン７ｇを成形安定剤として添加する。次いで、水６０ｇと活性物質であるエチレングリコール６ｍｌを添加してから攪拌してスラリーに入れて、フォームに十分に担持されるようにした後、フォームに担持されたスラリー中の約８０％程度を除去し乾燥させる。このようにポリウレタンフォームにスラリーを担持させる過程を３回繰り返して、全体重量が６ｇであるポリウレタンフォームにＹＫ−Ｒが担持された物質を得る。これを５０℃で２４時間乾燥した後、０．５℃／分の加熱速度で３００℃まで加熱してから３時間、１℃／分の加熱速度で９００℃まで加熱してから１時間焼結してフォーム１（濾過材１）を製造する。
コージアライト粉末を単独で使用してフォーム２（濾過材２／比較用）を製造した。
【００４５】
５−２．フロー−スロー形ハニカム（Flow-Through Honeycomb) 濾過材の製造
フロー−スローハニカム形濾過材は圧出法により製造し、その製造過程は次のようである。
ＹＫ−Ｒ粉末１００ｇにメチルセルロース４ｇをバインダーとして添加し、造孔材を１５ｇ加え、１時間ボールミルで乾式粉砕及び混合する。混合された原料に水を適量加えて０．８〜１ｍｇ／ｍｍ² の強度を有するようにスラリーを製造する。このスラリーをスクリュー圧出成形機に注入させながら直径５ｍｍのハニカムを成形した。成形された製品は７０℃の乾燥炉で３６時間乾燥させた後、図１に示すように多段階に昇温させながら焼結して完成した（濾過材３）。
又、コージアライト粉末を単独で使用して濾過材４（比較用）を製造した。
【００４６】
５−３．ウォールフローハニカム（Wall-Flow Honeycomb)形濾過材の製造
前記実施例５−２でＹＫ−Ｒを原料として製造されたフロースロー形ハニカムに、米国特許第４，４１１，８５６号のような方法のイージーキャスタブルポリマー（Easy Castable Polymer)で製作されたマスクを用いてハニカムと同材質のスラリーを押し入れて選択的に孔を塞ぐ方法によりウォールフローハニカム形濾過材５を製造した。
又、前記ＹＫ−Ｒとコージアライト粉末を１：１に混合し、前述した方法と同方法で濾過材６を製造し、コージアライト粉末を単独で使用してウォールフォローハニカム形濾過材７（比較用）を製造した。
【００４７】
実施例６．濾過体の製造
４００ｃｐｉのセラミックハニカムモノリスを２ｃｍ×２ｃｍ×２ｃｍの大きさに切る。ＹＫ−Ｒ粉末１０００ｇと水９００ｇを混合した後、粉砕機でスラリー状態に２４時間粉砕した。このスラリーを攪拌槽に移してから攪拌しながら濃酢酸とアンモニア水を添加してｐＨ４．５、粘度９５ｃｐｓに調節した。ここに準備したセラミックハニカムモノリスを浸してから、４０ｐｓｉの圧縮空気で吹き出し、２０℃／分の加熱速度で１２０℃まで加熱してから１０時間、５００℃で２時間加熱して、ＹＫ−Ｒ沈着支持体が１．３ｇ担持された濾過体８を製造した。
又、前記ＹＫ−Ｒとアルミナ粉末を１：１混合して、前述した方法と同方法で濾過体９を製造し、アルミナ粉末とチタニア粉末を単独で使用してそれぞれ濾過体１０，１１（比較用）を製造した。
【００４８】
実施例７．反応試験（濾過材及び濾過体）
７−１．ＣＯ酸化反応
前記実施例５と６で製造した濾過材及び濾過体１〜１１をそれぞれ反応器に装着した後、反応温度に調節する。ＣＯ２００ｐｐｍを含有した空気を空間速度５０，０００／ｈで反応器に流入させながら反応器の出口でのＣＯ濃度を時間分解結果で燃焼分析して転換率が５０％となる温度を調査する。
７−２．Ｃ₃ Ｈ₈ 酸化反応
前記ＣＯ酸化反応試験と同方法で１００ｐｐｍのＣ₃ Ｈ₈ と空気の混合ガスを流入させながらＣ₃ Ｈ₈ の転換率が５０％である温度を測定した。
【００４９】
７−３．ＳＯ₂ 酸化反応
前記ＣＯ酸化反応試験と同方法で５０ｐｐｍのＳＯ₂ と空気の混合ガスを流入させながら４５０℃でＳＯ₂ の転換率を測定する。
７−４．煤煙燃焼試験
前記実施例５と６で製造した濾過材１〜７及び濾過体８〜１１をそれぞれ煤煙１ｇと均一に充填してから反応器に装着する。温度を分当たり１０℃ずつ上昇して２００℃に到達したら、分当たり１℃ずつ昇温させて点火温度（煤煙燃焼温度）を測定した。
前記測定したＣＯとＣ₃ Ｈ₈ の５０％転換率、４５０℃でのＳＯ₂ 転換率及び煤煙燃焼温度を下記表５に示す。
【００５０】
実施例８．高温での耐久性評価
前記実施例５と６で製造した濾過材１〜７及び濾過体８〜１１を炉に入れた後、２０℃／分の加熱速度で８００℃まで加熱してから５時間放置した。
この触媒を実施例７と同方法でＣＯ、Ｃ₃ Ｈ₈ 、ＳＯ₂ 酸化反応活性と煤煙燃焼温度を測定した結果を下記表５に示す。
【００５１】
実施例９．硫黄酸化物に対する化学的安定性評価
前記実施例５と６で製造した触媒１〜７及び濾過体８〜１１を炉に入れた後、２０℃／分の加熱速度で５００℃に加熱し、ＳＯ₃ １，０００ｐｐｍを含有した窒素ガスを２リットル／分で５０時間流した。
この触媒を実施例７と同方法でＣＯ、Ｃ₃ Ｈ₈ 、ＳＯ₂ 酸化反応活性と煤煙燃焼温度を測定した結果を下記表５に示す。
【００５２】
【表５】

【００５３】
前記表５に示したように、ＹＫ−Ｒで製造された濾過材又は濾過体は単独でも既存の濾過材又は濾過体より煤煙の燃焼性能が優秀であるばかりでなく、高温で熱的安定性と硫黄酸化物による化学的安定性が卓越して、実際ディーゼル車両の粒子状物質を除去する触媒として優秀な耐久性を有することがわかる。
【００５４】
実施例１０．ＹＫ−Ｒから触媒体の製造
前記実施例５と６で製造された濾過材１〜７及び濾過体８〜１１に対してそれぞれ塩化白金酸水溶液を用いて、触媒金属含量が１ｗｔ％となるように担持した後、１２０℃で１２時間乾燥してから、２０℃／分の加熱速度で５００℃まで２時間焼成して触媒体１２〜２２を製造した。
【００５５】
実施例１１．反応試験（触媒体）
前記実施例１０で製造した触媒体１２〜２２についてそれぞれ実施例７と同方法で、ＣＯ、Ｃ₃ Ｈ₈ 及びＳＯ₂ 転換率及び煤煙燃焼温度を測定し、その結果を下記表８に示す。
【００５６】
実施例１２．高温での耐久性評価（触媒体）
前記実施例１０で製造した触媒材１２〜２２を６００℃で７日間空気中で焼成した。これら触媒体を実施例７と同方法でＣＯ、Ｃ₃ Ｈ₈ 及びＳＯ₂ の酸化反応と煤煙燃焼試験を実施し、その結果を下記表６に示す。
【００５７】
実施例１３．硫黄酸化物に対する化学的安定性評価（触媒体）
前記実施例１０で製造した触媒体１２〜２２を４００℃で７日間ＳＯ₂ ２００ｐｐｍが包含された乾燥空気中で焼成した。これら触媒を実施例７と同方法でＣＯ、Ｃ₃ Ｈ₈ 、ＳＯ₂ 酸化反応と煤煙燃焼試験を実施し、その結果を下記表６に示す。
【００５８】
【表６】

【００５９】
前記表６に示したように、廃触媒から製造された濾過材又は沈着支持体を用いて製造された触媒体は従来の触媒体に比べて大変低い温度でも粒子状物質を燃焼させて濾過材を再生させる優秀な触媒効果を奏し、さらに高温での熱的安定性と硫黄酸化物に対する化学的安定性が卓越することがわかる。
【００６０】
実施例１４．エンジン試験用触媒体の製造
米国コーニング社の商品名ＥＸ−５４セラミック単一体濾過機に下記表７に示したような沈着支持体を１リットル当たり１００ｇずつ沈着させた後、メタル含量が沈着支持体を基準として１ｗｔ％となるように触媒金属を担持した。これを１２０℃１２時間乾燥した後、５００℃空気中で２時間焼成して１〜６の六つの触媒体を製造した。
触媒体の耐久性を評価するために触媒体２，４に対して８００℃で７日間老化させ、ＳＯ₂ 被毒抵抗性を調査するために触媒体３，５及び６を２００℃出７日間２００ｐｐｍのＳＯ₂ に露出させた。
【００６１】
【表７】

【００６２】
実施例１５．触媒体の再生性能評価
前記実施例１４で製造した触媒体をそれぞれ英国、ペタース社（Petters Ltd.) のペターＡＶ−Ｂ（Petter AV-B)スーパーチャージド単一シリンダディーゼルエンジンに装着した後、運転速度２２５０ｒｐｍ、冷却水温度１００℃、オイル温度９０℃、オイル圧力２．５ｂａｒ、空気投入圧力２２３０ｍｂａｒ、電算運転条件でエンジンのバイパスバルブを閉め、濾過トラップバルブを開ける。スロットルを少し開け、再生現象が起こらない場合、スロットルをさらに開けて排気温度を上昇させながら触媒体の再生を実験した。再生が起こる時は、捕集された粒子状物質が触媒発火により燃焼して、エンジン排気管の背圧は減少し濾過トラップ後端の温度は上昇する。
【００６３】
又、排気ガス中の硫黄三酸化物の含量はイソプロピルアルコールと水の容積比が６０：４０である混合溶液に一定量の排気ガスを真空ポンプで２分間捕集しイオン液相クロマトグラフィー法で標準溶液と比較、分析した。
以上の試験方法で、前記実施例１４で製造された六つの触媒体に対して再生温度の硫黄三酸化物排出量を測定して下記表８に示す。
【００６４】
【表８】

【００６５】
前記表８で、触媒体１、２、３を比較して見ると、ＹＫ−Ｒ−１から製造された触媒体は高温又は硫黄酸化物に長時間露出されても触媒体の活性が減少しない卓越した耐久性を有することがわかる。
又、触媒体２、４を比較して見ると、高温で長時間露出された時、ＹＫ−Ｒ−１から製造された触媒体２がチタニアから製造された触媒体４に比べて低い再生温度と硫黄酸化物排出量を有することがわかる。
【００６６】
又、触媒体３、５、６を比較して見ると、硫黄酸化物に長時間露出された時、ＹＫ−Ｒ−１から製造された触媒体３がアルミナから製造された触媒体５、６に比べて低い再生温度と硫黄酸化物排出量を有することがわかる。
このように、ＹＫ−Ｒ−１から製造された触媒体は、従来の触媒体に比べて大変低い温度でも粒子状物質を燃焼させて濾過材を再生させる優秀な触媒効果を奏し、高温での熱的安定性と硫黄酸化物に対する化学的安定性が卓越して、実際ディーゼル車両の運転条件でも粒子状物質を除去する触媒として長期間にも優秀な性能を発揮することがわかる。
【００６７】
【発明の効果】
以上のような方法によりＹＫ−Ｒで製造された濾過材又は濾過体が含有された触媒体を濾過装置に装着し、ディーゼル車両の粒子状物質を除去する場合、粒子状物質に対する燃焼性能が優秀であるとともに高温での熱的安定性とディーゼル燃焼時に発生する硫黄酸化物に対する化学的安定性が卓越して、ディーゼル車両の粒子状物質を除去する性能を長期間維持させ得るので、ディーゼル車両粒子状物質の除去に適合する。
【図面の簡単な説明】
【図１】 実施例５の濾過材３の製造時の焼結条件を示す。[0001]
[Industrial application fields]
The present invention relates to a catalyst composition for purifying exhaust gas discharged from a diesel vehicle, a filter medium, a filter body and a catalyst body for removing particulate and gaseous substances in the exhaust gas using the composition, and a method for producing them. Is.
[0002]
[Prior art]
Particulate matter of exhaust gas discharged from diesel vehicles is unburned carbon particles having an average diameter of about 0.3 μm, soluble organic materials and sulfides, and the concentration of particulate matter is an environmental standard value (1993 heavy duty vehicle) In the case of exceeding the smog regulation value in the case of (40), not only visually unpleasant discomfort is caused, but also it is very harmful to the human body such as inducing cancer. In particular, Korea has emerged as a major cause of air pollution in Korea, where diesel vehicle ownership is 42% higher than any other country in the world. Strict emission control and purification of such particulate matter is required. Has been.
[0003]
In the case of heavy duty diesel vehicles, the emission control standard for particulate matter was 0.67 g / HP. Hour (0.1 g / HP. Hour in the United States since 1994) is a trend that gradually strengthens every year, and therefore various studies for removing particulate matter emitted by diesel vehicles are being actively conducted.
The direction of development of particulate matter removal technology is broadly divided into the suppression of the generation of unburned substances by improving the engine, the improvement of combustion efficiency using fuel additives, and the post-treatment of particulate substances.
[0004]
Engine improvement and fuel additive utilization can improve combustion efficiency in the engine and reduce harmful substances such as particulate matter or soot, but it is expensive and technical. The situation is difficult to completely suppress due to limitations, and generally a removal method using post-processing techniques is used.
The post-processing technology consists of a filtration technology that filters particulate matter in the exhaust gas and a regeneration technology that burns the filtered particulate matter and regenerates the filter media, and the filtration technology consists of particulate matter in the exhaust gas. We are focusing on research to select a filter material with excellent performance that can effectively collect and apply it to actual vehicles.
[0005]
On the other hand, the filter media is damaged by the increase in the back pressure in the engine exhaust passage due to the filtration of the particulate matter, the performance of the engine is reduced, and when the collected particulate matter is burned under high temperature conditions, the filter media is subjected to thermal shock. Given that the problem of durability is serious, it has become necessary to develop a regeneration technology for effectively burning particulate matter at low temperatures. The most widely known regeneration technologies to date include a method of regenerating by supplying secondary energy from the outside using a burner, a heater, etc. or increasing the exhaust gas temperature by throttling, and adding a catalyst to the fuel or a catalyst. There is a method of regenerating at a relatively low temperature by reducing the activation energy of the oxidation reaction by supporting the catalyst on a filter medium.
[0006]
In the present invention, among these techniques, a method for removing particulate matter by catalytic action has been particularly studied, which is a ceramic foam, a wire mesh, a metal foam, a wall flow ceramic honeycomb, an open flow ceramic honeycomb or a metal honeycomb. A catalyst material capable of burning particulate matter is supported on a filter medium containing a fire-resistant three-dimensional structure, and fine particulate matter contained in the exhaust gas of a diesel engine is filtered, and exhaust gas in a normal diesel engine operation state Combusting particulate matter under exhaust conditions (gas composition and temperature).
[0007]
The general required performance of the exhaust gas purifying catalyst for diesel engines is as follows. First, not only carbon fine particles but also human harmful components such as unburned hydrocarbons can be removed with high efficiency by combustion even at low temperatures, and second, sulfur components contained in large amounts in light oil used as fuel SO generated in the engine from ₂ Is SO _Three Has low activity to be oxidized to SO in exhaust gas _Three The third is SO ₂ The catalyst is not deactivated by a poisoning agent such as the above, and fourthly, it has durability that is not deactivated even when continuously used at a high temperature.
[0008]
Various methods have been proposed to improve the removal efficiency of particulate matter by combustion. In these conventional methods, in order to provide a wide reaction surface area, a platinum group metal known as a particulate matter combustion catalyst is prepared by preliminarily depositing a deposition support such as activated alumina or titania on a filter medium as a catalyst carrier. Is used in which the aqueous solution is uniformly supported on the filter with a platinum group salt aqueous solution.
[0009]
[Problems to be solved by the invention]
However, the kind, amount and production method of such a deposition support and catalyst component did not always give a satisfactory catalytic effect.
That is, in the case of the general alumina, it is thermally stable at a high temperature of about 800 ° C. and has sufficient durability for continuous use at a high temperature, but combustion of sulfur components contained in a large amount in light oil. It reacts with the sulfur trioxide discharged from the catalyst to form aluminum sulfate, causing a change in the surface area and pore structure, thereby causing a problem that the activity of the catalyst using alumina as a carrier is drastically lowered.
[0010]
Further, in the case of the above conventional titania, it is chemically stable with respect to sulfur trioxide, and the decrease in activity due to sulfur trioxide is small. When the exhaust gas temperature deteriorates at an operating condition of about 300 to 600 ° C., particularly when it is repeatedly exposed to the burning of soot, that is, the rapid increase in temperature at the time of regeneration of the filter medium, the surface area reduction and phase change of titania (ie There is a drawback that the activity and durability are lowered by the destruction of the pore structure from the anatase form to the crystalline rutile form).
[0011]
As described above, a catalyst that completely satisfies the four performances required as a diesel engine exhaust gas purification catalyst has not been reported yet.
Therefore, the object of the present invention is, first of all, to maintain a high catalytic effect at a high temperature for a long period of time, and the sulfur oxide produced in the engine does not reduce the activity of the catalyst. It is an object of the present invention to provide a catalyst composition having excellent combustion performance of particulate matter discharged from a diesel vehicle and a method for producing the same.
[0012]
Secondly, the present invention provides a filter medium having excellent performance for removing particulate matter from diesel vehicles using the catalyst composition and a method for producing the same.
Thirdly, when the particulate matter of the diesel vehicle is to be removed using the existing filter medium, the filter body on which the deposition support body having the same effect as the filter medium described above for the second purpose is deposited. And a method of manufacturing the same.
Fourthly, it is to provide a diesel engine particulate matter removing catalyst body using the filter medium or filter body described above for the above purpose and a method for producing the same.
[0013]
[Means for Solving the Problems]
As a result of many experiments and researches, the present inventors have achieved an excellent catalytic effect for removing particulate matter discharged from diesel vehicles, discovered catalyst components having the above catalyst requirements, Since a large amount of such a catalyst component is contained in the waste catalyst discharged in the desulfurization process in the oil cracking facility, the filter medium or the deposition support produced using such a waste catalyst as a raw material is smoking alone. The catalyst body in which at least one platinum group metal selected from the platinum group metal is dispersed and supported on such a filter medium or deposition support is deposited on the support medium. The present invention was completed by discovering the fact that the thermal stability at high temperatures and the chemical stability to sulfur trioxide can be significantly improved over the existing catalyst bodies produced as:
[0014]
The catalyst used in the desulfurization process in the heavy oil cracking facility of an essential oil factory is generally composed of 30 to 50% aluminum, 0 to 10% molybdenum, 0 to 3% nickel, 0 to 3% phosphorus, etc. However, by using it in the desulfurization process, other catalyst components such as vanadium and cobalt, which have an excellent effect on particulate matter combustion, are added in addition to such catalyst components. Discharged.
The composition of the waste catalyst varies depending on the operating conditions of the desulfurization process, the period of use, the composition of the crude oil and the desulfurization catalyst, etc., but in general, vanadium 80% or less, molybdenum 80% or less, nickel 20% or less, cobalt 30 % Or less, aluminum 99% or less, and impurities during normal crude oil refining.
[0015]
The method for producing a diesel vehicle particulate matter removing catalyst composition for achieving the first object of the present invention,
a) heating and pre-treating the waste catalyst used as a raw material;
b) A step of pulverizing the waste catalyst in the step a) to produce a waste catalyst powder.
The waste catalyst used as the raw material is a waste catalyst generally discharged in a desulfurization process in a heavy oil decomposition facility of an essential oil factory, and contains impurities such as moisture or oil. The waste catalyst is heated at 400 to 1000 ° C. in an oxygen atmosphere for 0.5 to 5 hours, and pulverized into 100 to 800 mesh particles by a pulverizer to produce a waste catalyst powder.
[0016]
The waste catalyst pretreated in this way is used as a filter medium, a deposition support and a raw material for producing the catalyst body (hereinafter referred to as YK-R) for achieving the object of the present invention.
At this time, if the heating temperature is 400 ° C. or less, the heating is insufficient and impurities are not completely removed. If the heating temperature is 1000 ° C. or more, not only energy is wasted but also deterioration of the catalyst components in the waste catalyst is accelerated. In addition, if the particle size is too large, it is difficult to obtain a uniformly mixed slurry at the next stage of slurry production, and if the particle size is too small, not only the production cost increases but also durability at high temperatures. Sexuality decreases.
[0017]
In order to achieve the second object of the present invention, a method for producing a filter material for removing diesel vehicle particulate matter,
a) A step of producing a filter medium slurry by mixing YK-R powder alone or an existing filter medium powder with YK-R powder;
b) forming a filter medium slurry into a filter medium structure;
c) As a result of step b), the product is sintered to produce a filter medium.
[0018]
The filter medium slurry is prepared by thoroughly mixing an adhesive, a molding stabilizer (Attacking Agent), an active substance, water, and the like with the YK-R powder or a mixture of the YK-R powder and the existing filter medium powder.
As the existing filter medium powder used in the present invention, all the materials already known as the production raw materials for ceramic filter media such as cordierite, mullite, zirconia, silica and the like can be used, and there is no particular limitation.
Further, the mixing composition of YK-R powder and existing filter medium powder is suitably 10 to 100% in the case of YK-R powder, and 0 to 90% is appropriate in the case of existing filter medium powder.
When the content of the YK-R powder is less than 10%, the concentration of the catalyst substance described above is small and the activity is lowered.
[0019]
The adhesive used in the present invention is useful for curing a ceramic material, and all known substances can be used, and there is no particular limitation on this.
The molding stabilizer used in the present invention is useful for the prevention of a cylindrical foam (Tubular Foam) of ceramic material, and all already known substances can be used, and there is no particular limitation.
The active substance used in the present invention is useful for controlling the pores of the ceramic material, and all already known substances can be used, and there is no particular limitation on this.
[0020]
The produced filter medium slurry is formed into a filter body structure by a known method useful for forming a ceramic material such as injection, extrusion, etc., and after completely drying at 25 to 150 ° C., 200 to 1000 ° C. To produce a filter medium.
The filter medium of the present invention is useful for filtering particulate matter of diesel vehicles such as ceramic foam, open flow honeycomb, ceramic fiber filter, ceramic honeycomb, wall flow honeycomb monolith, etc., and can use all already known three-dimensional structures. There are no special restrictions on this.
[0021]
In order to achieve the third object of the present invention, a method for producing a filter body on which a diesel vehicle particulate matter removal deposition support is deposited,
a) mixing YK-R powder alone or YK-R powder with existing deposition support powder to produce a deposition support slurry;
b) depositing a deposition support slurry on an existing filter media structure;
c) As a result of step b), the product is heated to produce a filter body.
[0022]
The present invention provides a deposition support that exhibits the same excellent performance as that of the above-described filter produced by YK-R even when it is intended to remove particulate matter from a diesel vehicle using an existing filter medium. To do.
As the existing deposition support powder used in the present invention, all materials already known as a production raw material for the deposition support can be used as zeolite such as alumina, titania, silica and the like, and there is no particular limitation.
Further, the mixing composition of YK-R powder and existing deposition support powder is suitably 10 to 100% in the case of YK-R powder, and 0 to 90% in the case of existing deposition support.
If the content of the YK-R powder is less than 10%, the concentration of the catalyst material described above is small and the activity is lowered.
[0023]
The deposition support slurry is adjusted so that the viscosity is 400 cps or less by adding water to the YK-R powder or the mixture of YK-R powder and deposition support powder and mixing uniformly, and then adding an acid or base. To manufacture.
The composition of the deposition support powder in the deposition support slurry is suitably 3 to 50% by weight.
In the slurry, when the content of the deposition support powder is less than 3%, the content of the catalyst component is small and it is difficult to achieve a catalytic effect. When the content is 50% or more, the deposition support powder is excessively dispersed and the viscosity is uniform. It is difficult to produce a low deposition support slurry.
Moreover, when the viscosity is 400 cps or more, it is difficult to uniformly coat the deposition support on the filter body.
[0024]
The form of the filter material used in the present invention is useful as a particulate matter filter material for diesel vehicles such as ceramic foam, open flow honeycomb, ceramic fiber filter, ceramic honeycomb, metal foam, wall flow honeycomb monolith, metal mesh, etc. Thus, all already known three-dimensional structures can be used, and there are no special restrictions.
[0025]
5 to 200 g per 1 liter of the filter medium is deposited on the filter medium and dried, and sintered at 400 to 1000 ° C. to produce a filter body. At this time, if the amount of the deposited support slurry is 5 g / liter or less, a sufficient surface area cannot be provided, and the catalyst performance is lowered due to a low concentration of the catalyst substance. If the amount is 200 g / liter or more, the exhaust gas pressure is excessively increased. To reduce the driving efficiency.
In order to provide a sufficient surface area, it is also possible to deposit the deposition support on the filter medium made of YK-R as described above.
[0026]
In order to achieve the fourth object of the present invention, a method for producing a diesel vehicle particulate matter removing catalyst body of the present invention comprises:
a) supporting a catalyst metal on a filter medium or filter body manufactured to achieve the second and third objects;
b) The product of step a) is calcined to produce a catalyst body.
After the solution containing the catalyst metal is supported on the filter medium or the filter body, the catalyst body in the form of metal or metal oxide is finally produced by heating and baking at 400 to 800 ° C., for example.
[0027]
The catalyst metal of the present invention is at least one platinum group metal solution selected from platinum group metal compounds such as platinum, rhodium or palladium, and the content of platinum, rhodium or palladium is preferably 0 to 7 platinum per liter of the filter medium. 0.07 g, rhodium 0-2 g, palladium 0-7.07 g (but the total amount of these metals is greater than 0).
[0028]
The ratio of the amount of the at least one noble metal selected from platinum, rhodium and palladium deposited on the deposition support (non-metal / deposition support weight ratio) is in the range of 0.001 / 1 to 0.1 / 1. Is desirable.
When the ratio of the amount of the noble metal supported on the deposition support is 0.001 / 1 or less, the amount of the noble metal supported is too small to expect the catalytic effect of the noble metal. Since there is almost no increase in the effect and only the cost of the precious metal is increased, it is disadvantageous both in terms of economy and effective use of resources.
[0029]
【Example】
Hereinafter, the configuration and effects of the present invention will be described in detail according to examples. However, the following examples do not limit the scope of the present invention.
[0030]
【Example】
Example 1. Method for producing catalyst component (YK-R)
1-1. Composition analysis of raw catalyst and waste catalyst (YK-R)
In the hydrodesulfurization process in the heavy oil cracking facility of Yuko Co., Ltd., after filling the catalyst as shown in Table 1 and operating the process for 250 days, take 2 g of the discharged waste catalyst and take ICP ( Table 2 below shows the results of component analysis by Induction Coupled Plasma) and comparison with the composition of the catalyst initially charged.
[0031]
[Table 1]

[0032]
[Table 2]

[0033]
1-2. Change in specific surface area due to heating temperature
After taking 10 g of the waste catalyst and heating it as shown in Table 3 below, the specific surface area was measured.
It can be seen that when the heating temperature is 400 ° C. or lower, the heating is insufficient and impurities are not completely removed, and when the heating temperature is 1000 ° C. or higher, the pores are destroyed due to deterioration of the catalyst component.
[0034]
[Table 3]

[0035]
1-3. Production of catalyst composition (YK-R) powder
100 kg of the waste catalyst was heated in a furnace at a heating rate of 20 ° C./min to 800 ° C., then heated for 2 hours, cooled, and pulverized with a pulverizer to produce a 200 mesh powder.
[0036]
Example 2 Reaction test (YK-R composition)
2-1. Sample preparation
15 g each of YK-R powder produced in Example 1-3, alumina, and titania were taken to prepare Composition 1 (for implementation) and Compositions 2 and 3 (for comparison), respectively.
2-2. CO oxidation reaction
The composition samples 1 to 3 produced in Example 2-1 are each charged with 1 g in a reactor and fixed, and then adjusted to the reaction temperature. While the air containing 200 ppm of CO is introduced into the reactor at a space velocity of 50,000 / h, the concentration of CO is analyzed at the outlet of the reactor by the time-resolved result, and the temperature at which the conversion rate becomes 50% is investigated.
[0037]
2-3. C _Three H ₈ Oxidation reaction
1000 ppm C by the same method as the CO oxidation reaction test. _Three H ₈ C and a mixed gas of air _Three H ₈ The temperature at which the conversion of is 50% is measured.
2-4. SO ₂ Oxidation reaction
50 ppm SO by the same method as the CO oxidation reaction test. ₂ And a mixed gas of air and SO at 450 ° C. ₂ Measure the conversion rate.
[0038]
2-5. Smoke combustion test
The composition samples 1 to 3 prepared in Example 2-1 are uniformly mixed with 1 g of particulate matter in the smoke, and then charged into the reactor. When the temperature was increased by 10 ° C. per minute to reach 200 ° C., the temperature at which ignition was performed (soot combustion temperature) was measured while increasing the temperature by 1 ° C. per minute.
The measured CO and C _Three H ₈ 50% conversion of SO at 450 ° C ₂ The conversion rate and smoke combustion temperature are shown in Table 4 below.
[0039]
Example 3 Durability evaluation at high temperature
5 g of each catalyst composition 1-3 created in Example 2-1 was placed in a furnace, heated to 800 ° C. at a heating rate of 20 ° C./min, and allowed to stand for 5 hours.
This catalyst composition was treated in the same manner as in Example 2 with CO, C _Three H ₈ , SO ₂ The results of measuring the oxidation reaction activity and the smoke combustion temperature are shown in Table 4 below.
[0040]
Example 4 Chemical stability evaluation for sulfur oxides
After taking 5 g each of the catalyst 1-3 produced in Example 2-1 and putting it in the furnace, it was heated to 500 ° C. at a heating rate of 20 ° C./min. _Three Nitrogen gas containing 100 ppm was flowed at 2 liters / minute for 50 hours.
This catalyst was treated in the same manner as in Example 2 with CO, C _Three H ₈ , SO ₂ The results of measuring the oxidation reaction activity and the smoke combustion temperature are shown in Table 4 below.
[0041]
[Table 4]

[0042]
As shown in Table 4 above, YK-R (waste catalyst composition) powder (sample 1) alone has not only excellent smoke combustion performance, but also thermal stability at high temperatures and chemistry by sulfur oxides. It can be seen that the mechanical stability is excellent, and in fact, it has excellent durability as a catalyst composition for removing particulate matter of diesel vehicles.
[0043]
Embodiment 5 FIG. Filter media production
5-1. Manufacture of foam filter media
A 10 ppi polyurethane foam was cut into a size of 2 cm × 2 cm × 2 cm, then supported on a solution having a weight ratio of water to methyl alcohol of 1: 1 for 10 minutes, and then dried.
[0044]
After adding 15 g of dextrin as a binder to 100 g of YK-R produced in Example 1-3, 7 g of monoethanolamine is added as a molding stabilizer. Next, after adding 60 g of water and 6 ml of the active substance ethylene glycol, the mixture was stirred and put into the slurry so that it was sufficiently supported on the foam, and about 80% of the slurry supported on the foam was removed. Remove and dry. The process of supporting the slurry on the polyurethane foam in this manner is repeated three times to obtain a substance in which YK-R is supported on the polyurethane foam having an overall weight of 6 g. This was dried at 50 ° C. for 24 hours, heated to 300 ° C. at a heating rate of 0.5 ° C./min, then heated to 900 ° C. at a heating rate of 1 ° C./min for 1 hour and then sintered for 1 hour. Thus, foam 1 (filter material 1) is produced.
Foam 2 (filter medium 2 / comparative) was produced using cordierite powder alone.
[0045]
5-2. Manufacture of Flow-Through Honeycomb filter media
The flow-slow honeycomb filter medium is manufactured by an extrusion method, and the manufacturing process is as follows.
4 g of methylcellulose is added as a binder to 100 g of YK-R powder, 15 g of a pore former is added, and dry pulverization and mixing are performed with a ball mill for 1 hour. Add an appropriate amount of water to the mixed raw material and add 0.8 to 1 mg / mm ² A slurry is produced so as to have the following strength. A honeycomb having a diameter of 5 mm was formed while this slurry was poured into a screw extrusion molding machine. The molded product was dried for 36 hours in a drying oven at 70 ° C., and then sintered and completed while raising the temperature in multiple stages as shown in FIG. 1 (filter material 3).
Moreover, the filter medium 4 (for comparison) was manufactured by using cordierite powder alone.
[0046]
5-3. Manufacture of Wall-Flow Honeycomb filter media
A mask made of Easy Castable Polymer according to the method of US Pat. No. 4,411,856 is applied to the flow throw type honeycomb manufactured using YK-R as a raw material in Example 5-2. The wall flow honeycomb filter medium 5 was manufactured by a method in which a slurry of the same material as that of the honeycomb was pressed and the pores were selectively closed.
Further, the YK-R and cordierite powder are mixed at a ratio of 1: 1, and the filter medium 6 is manufactured by the same method as described above. The wall follow honeycomb filter medium 7 is obtained by using the cordierite powder alone. (For comparison) was manufactured.
[0047]
Example 6 Manufacture of filter body
A 400 cpi ceramic honeycomb monolith is cut to a size of 2 cm × 2 cm × 2 cm. After mixing 1000 g of YK-R powder and 900 g of water, it was pulverized in a slurry state for 24 hours with a pulverizer. The slurry was transferred to a stirring tank, and concentrated acetic acid and aqueous ammonia were added while stirring to adjust the pH to 4.5 and the viscosity to 95 cps. After immersing the prepared ceramic honeycomb monolith, it was blown out with compressed air of 40 psi, heated to 120 ° C. at a heating rate of 20 ° C./min, then heated at 500 ° C. for 2 hours to deposit YK-R A filter body 8 carrying 1.3 g of a support was produced.
Further, the YK-R and alumina powder are mixed 1: 1, and the filter body 9 is manufactured by the same method as described above, and the filter bodies 10 and 11 are respectively compared using the alumina powder and titania powder alone (comparison). Manufactured).
[0048]
Example 7 Reaction test (filter material and filter)
7-1. CO oxidation reaction
The filter medium and the filter bodies 1 to 11 produced in Examples 5 and 6 are respectively attached to the reactor, and then adjusted to the reaction temperature. The temperature at which the conversion rate is 50% is investigated by performing combustion analysis on the CO concentration at the outlet of the reactor by the time-resolved result while flowing air containing 200 ppm of CO into the reactor at a space velocity of 50,000 / h.
7-2. C _Three H ₈ Oxidation reaction
100 ppm of C by the same method as the CO oxidation reaction test. _Three H ₈ C and a mixed gas of air _Three H ₈ The temperature at which the conversion of was 50% was measured.
[0049]
7-3. SO ₂ Oxidation reaction
50 ppm SO by the same method as the CO oxidation reaction test. ₂ And a mixed gas of air and SO at 450 ° C. ₂ Measure the conversion rate.
7-4. Smoke combustion test
The filter media 1 to 7 and the filter media 8 to 11 produced in Examples 5 and 6 are uniformly filled with 1 g of smoke, and then attached to the reactor. When the temperature was increased by 10 ° C. per minute to reach 200 ° C., the temperature was increased by 1 ° C. per minute and the ignition temperature (smoke combustion temperature) was measured.
The measured CO and C _Three H ₈ 50% conversion of SO at 450 ° C ₂ The conversion rate and smoke combustion temperature are shown in Table 5 below.
[0050]
Example 8 FIG. Durability evaluation at high temperature
The filter media 1 to 7 and the filter bodies 8 to 11 manufactured in Examples 5 and 6 were placed in a furnace, heated to 800 ° C. at a heating rate of 20 ° C./min, and left for 5 hours.
This catalyst was treated in the same manner as in Example 7 with CO, C _Three H ₈ , SO ₂ The results of measuring the oxidation reaction activity and the smoke combustion temperature are shown in Table 5 below.
[0051]
Example 9 Chemical stability evaluation for sulfur oxides
After putting the catalysts 1 to 7 and the filter bodies 8 to 11 produced in Examples 5 and 6 into a furnace, they were heated to 500 ° C. at a heating rate of 20 ° C./min, and SO _Three Nitrogen gas containing 1,000 ppm was flowed at 2 liters / minute for 50 hours.
This catalyst was treated in the same manner as in Example 7 with CO, C _Three H ₈ , SO ₂ The results of measuring the oxidation reaction activity and the smoke combustion temperature are shown in Table 5 below.
[0052]
[Table 5]

[0053]
As shown in Table 5 above, the filter medium or filter body produced with YK-R alone has not only excellent smoke combustion performance than the existing filter medium or filter body, but also has thermal stability at high temperatures. It can be seen that the chemical stability due to sulfur oxides is excellent, and in fact, it has excellent durability as a catalyst for removing particulate matter from diesel vehicles.
[0054]
Example 10 Production of catalyst body from YK-R
After carrying | supporting so that a catalyst metal content might be 1 wt% using the chloroplatinic acid aqueous solution with respect to the filter media 1-7 and the filter bodies 8-11 which were manufactured in said Example 5 and 6, respectively, at 120 degreeC. After drying for 12 hours, catalyst bodies 12 to 22 were produced by calcination to 500 ° C. for 2 hours at a heating rate of 20 ° C./min.
[0055]
Example 11 Reaction test (catalyst)
For the catalyst bodies 12 to 22 produced in Example 10, the same methods as in Example 7 were used. _Three H ₈ And SO ₂ The conversion rate and smoke combustion temperature were measured, and the results are shown in Table 8 below.
[0056]
Example 12 Durability evaluation at high temperature (catalyst)
Catalyst materials 12 to 22 produced in Example 10 were calcined in air at 600 ° C. for 7 days. These catalyst bodies were treated in the same manner as in Example 7 with CO, C _Three H ₈ And SO ₂ The oxidation reaction and the soot combustion test were conducted, and the results are shown in Table 6 below.
[0057]
Example 13 Chemical stability evaluation for sulfur oxide (catalyst)
The catalyst bodies 12 to 22 prepared in Example 10 were SO treated at 400 ° C. for 7 days. ₂ Firing in dry air containing 200 ppm. These catalysts were prepared in the same manner as in Example 7 with CO, C _Three H ₈ , SO ₂ An oxidation reaction and a soot combustion test were conducted, and the results are shown in Table 6 below.
[0058]
[Table 6]

[0059]
As shown in Table 6, the filter medium manufactured from the waste catalyst or the catalyst body manufactured using the deposition support body burns the particulate matter even at a very low temperature as compared with the conventional catalyst body, and the filter medium. It can be seen that it has an excellent catalytic effect to regenerate, and has excellent thermal stability at high temperatures and chemical stability against sulfur oxides.
[0060]
Example 14 Manufacture of catalyst bodies for engine testing
After depositing 100 g per liter of deposition support as shown in Table 7 below on a product name EX-54 ceramic single body filter manufactured by Corning, USA, the metal content becomes 1 wt% based on the deposition support. Thus, a catalytic metal was supported. This was dried at 120 ° C. for 12 hours and then calcined in air at 500 ° C. for 2 hours to produce six catalyst bodies 1 to 6.
In order to evaluate the durability of the catalyst bodies, the catalyst bodies 2 and 4 were aged at 800 ° C. for 7 days, and SO ₂ In order to investigate the poisoning resistance, catalyst bodies 3, 5 and 6 were subjected to 200 ppm SO for 7 days at 200 ° C. ₂ Exposed to.
[0061]
[Table 7]

[0062]
Example 15. Evaluation of regeneration performance of catalyst body
After the catalyst body produced in Example 14 was mounted on a Petter AV-B supercharged single cylinder diesel engine of Petters Ltd., UK, an operating speed of 2250 rpm and a cooling water temperature The engine bypass valve is closed and the filtration trap valve is opened at 100 ° C., oil temperature 90 ° C., oil pressure 2.5 bar, air input pressure 2230 mbar, and computer operation conditions. When the throttle was opened slightly and the regeneration phenomenon did not occur, the regeneration of the catalyst body was experimented while further increasing the exhaust temperature by opening the throttle further. When regeneration occurs, the collected particulate matter burns due to catalytic ignition, the back pressure of the engine exhaust pipe decreases, and the temperature at the rear end of the filter trap rises.
[0063]
Also, the content of sulfur trioxide in the exhaust gas is determined by ionic liquid phase chromatography by collecting a certain amount of exhaust gas with a vacuum pump for 2 minutes in a mixed solution with a volume ratio of isopropyl alcohol and water of 60:40. Comparison and analysis with standard solution.
With the above test method, the sulfur trioxide discharge amount at the regeneration temperature was measured for the six catalyst bodies manufactured in Example 14, and the results are shown in Table 8 below.
[0064]
[Table 8]

[0065]
In Table 8, the catalyst bodies 1, 2, and 3 are compared, and the activity of the catalyst body produced from YK-R-1 does not decrease even when exposed to high temperature or sulfur oxide for a long time. It can be seen that it has excellent durability.
Further, when the catalyst bodies 2 and 4 are compared, the catalyst body 2 produced from YK-R-1 has a lower regeneration temperature than the catalyst body 4 produced from titania when exposed at a high temperature for a long time. And sulfur oxide emissions.
[0066]
Further, when the catalyst bodies 3, 5 and 6 are compared, the catalyst body 3 produced from YK-R-1 is produced from alumina when exposed to sulfur oxide for a long time. It can be seen that it has a lower regeneration temperature and sulfur oxide emission than
As described above, the catalyst body manufactured from YK-R-1 has an excellent catalytic effect of regenerating the filter medium by burning particulate matter even at a very low temperature as compared with the conventional catalyst body. It can be seen that the thermal stability and chemical stability against sulfur oxides are excellent, and in fact, they exhibit excellent performance as a catalyst for removing particulate matter even under the operating conditions of diesel vehicles.
[0067]
【The invention's effect】
When the filter medium manufactured by YK-R by the above method or the catalyst body containing the filter body is attached to the filter device and the particulate matter of the diesel vehicle is removed, the combustion performance against the particulate matter is excellent. In addition, the thermal stability at high temperatures and the chemical stability against sulfur oxides generated during diesel combustion are excellent, and the performance of removing particulate matter from diesel vehicles can be maintained for a long time. Suitable for removal of particulate matter.
[Brief description of the drawings]
FIG. 1 shows sintering conditions during production of a filter medium 3 of Example 5.

Claims (16)

Waste catalyst for removing particulate matter from diesel engines containing vanadium 80% or less, molybdenum 80% or less, nickel 20% or less, cobalt 30% or less, alumina 99% or less, and trace impurities included in normal crude oil refining A method for producing a composition comprising the following steps (i) and (ii):
(I) heat treating the waste catalyst discharged from the desulfurization process of the heavy oil cracking facility at 400 to 1000 ° C. for 0.5 to 5 hours;
(Ii) pulverizing the heat-treated waste catalyst to 100-800 mesh A step of producing a slurry containing the waste catalyst composition produced by the method according to claim 1 alone or a mixed material of the waste catalyst composition and a powder for producing a filter medium,
Forming the slurry into a filter media structure; and
A method for producing a filter material for removing particulate matter from a diesel engine, comprising the step of sintering the filter material structure at 400 to 1000 ° C. The filter material producing powder is at least selected from the group consisting of cordierite, mullite, zirconia and silica. 1 The method for producing a filter material for removing particulate matter from a diesel engine according to claim 2 or 3, wherein the seed material is a seed. The waste catalyst composition and the filter material producing powder are present in the slurry at a weight ratio of 10 to 100% and 0 to 90%, respectively. The manufacturing method of the filter material for particulate matter removal of the diesel engine as described in 2. The filter media structure is selected from the group consisting of ceramic foam, open flow honeycomb, ceramic fiber filter, ceramic honeycomb and wall flow honeycomb monolith. 1 The method for producing a filter material for removing particulate matter from a diesel engine according to claim 2, wherein the seed material is a seed. A filter material for removing particulate matter from a diesel engine, which is produced by the method according to any one of claims 2 to 5. The waste catalyst composition produced by the method according to claim 1 alone, or a mixed material of the waste catalyst composition and the deposition support powder is mixed with water and then mixed with an acid or a base to support deposition. Producing a body slurry;
Depositing the deposition support slurry on a filter media structure; and
A method for producing a filter medium on which a deposit support for removing diesel engine particulate matter is deposited, comprising the step of sintering the deposited filter medium structure at 400 to 1000 ° C. At least the deposition support powder is selected from the group consisting of alumina, titania and silica. 1 The method for producing a filter medium on which a particulate matter removal deposition support for a diesel engine according to claim 7 is deposited. 9. The waste catalyst composition and the deposition support powder are present in a weight ratio of 10 to 100% and 0 to 90%, respectively, in the deposition support slurry. The manufacturing method of the filter medium in which the deposition support body for particulate matter removal of a diesel engine was deposited. The filter medium structure is at least selected from the group consisting of ceramic foam, open flow honeycomb, ceramic fiber filter, ceramic honeycomb, metal mesh, metal foam, and warm flow honeycomb monolith. 1 Claim characterized by the species Item 10. A method for producing a filter medium on which the particulate matter removing deposition support body according to any one of Items 7 to 9 is deposited. 11. The particulate matter removal deposition support for a diesel engine according to claim 7, wherein the deposition support is deposited in an amount of 5 to 200 g per liter of a filter medium structure. A method for producing a filter medium. A filter medium on which a deposition support for removing diesel engine particulate matter, which is produced by the method according to any one of claims 7 to 11, is deposited. A platinum group selected from the group consisting of platinum, palladium, and rhodium on the filter medium produced by the method according to claim 2 or the filter medium on which the deposition support produced by the method according to claim 7 is deposited. Carrying a metal component;
A method for producing a catalyst body for removing particulate matter from a diesel engine, comprising the steps of heating and firing the filter medium carrying the metal component at 400 to 1000 ° C. The content of the supported metal component is 0 to 7.07 g of platinum, 0 to 7.07 g of palladium or 0 to 2 g of rhodium per liter of the filtering material on which the filtering material or the deposition support is deposited, The method for producing a catalyst body for removing particulate matter from a diesel engine according to claim 13, wherein the total amount of these metals is greater than zero. 14. For removing particulate matter from a diesel engine according to claim 13, wherein the weight ratio of the metal to the deposition support (platinum group metal / deposition support) is 0.001 / 1 to 0.1 / 1. A method for producing a catalyst body. A diesel engine particulate matter removing catalyst body manufactured by the method according to any one of claims 13 to 15.

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